Vat dyestuffs of the polynuclear aromatic imidazole series and the process of preparing them



UNHE

ia'zaaae Iw'l'AXl'IaIILIAI-I PAUL SCHMIDT AND WILI-IELIVI NEUGEBAUER, OF BIEI BRICH-ON- T HE- REINE, GERMANY, ASSIGNOB-S T0 GENERAL ANILINE WORKS, INC., OF NEW YORK,

N. Y., A CORPORATION OF DELAWARE VAT DYESTUFFS on THE ronvnuonnlaa Anor/rArrc IMIDAZOLE SERIES-AND THE rnoonss on PREPARING THEM No Drawing. Application filed February 1, 1929, Serial No. 336,915, and. Germany December 27, 1922.

Our present invention relates to vat dyestuffs and process of preparing them.

We have found that compounds of the following constitution:

- N N N 6/ I I I lent substituent, such as chlorine can be caused to react with phenols, thiophenols, amines, alcohols,'and inercaptans so as to form valuable vat dyestufi's.

The conversioncan be effected by heating the components alone or in the presence of a solvent or a diluent. Acid-binding substances and also catalysts, such as for instance copper compounds, may be added. Y

The products of the above general formulae (A()) which are used as starting materials can be obtained by condensing with ortho diamines negatively substituted perylene-3.- 4.9.10-tetracarboxylic acids and their monoiinides respectively, or by subsequently introducing negative substituentsinto the products obtainable by condensing perylene- 3.4.9.10-tetracarboxylic acid or a monoimide are heated to the boiling'point for 910 hours with 100 parts of phenol and 10' parts of potassium hydroxide in a vessel provided with a stirrer and reflux condenser. r

The reaction product may be isolated from the melt after the latter has been sufficiently cooled, for instance by means of d lute caustic soda soiuti on which causes the phenol to dissoive. The mass is then filtered, washed and dried. it The dyestuff, thus obtained in the form of a bluish-black powder, is soluble in concentrated sulfuric acid to a blue solution.

The hydrosulfite vat is of-a green color and dyes cotton fast blue tints. The parent dye- 7 stuff dyes bluish-violet tints.

' In the present example cresol and other aromatic hydroxycompounds can be substituted for the phenol, the reaction taking place in an analogous manner; thiophenol or similar r thiocompounds can also be used.

I The final product has the following formula: I V v 2. 10 parts of the violet vat-dyestuff of the following formula: 8 1

(obtainable by condensing dichlorperylene- 3.4.9.10-tetracarboxylic .acid anhydride with o-phenylenediamine) are heated to the boiling point with 100 parts of phenol and 10 parts of anhydrous potassium carbonate and boiling is continued for 20 hours While stirring.. The working up of the melt can take place as described in Example 1.- The bluish-black dyestufi-powder, thus obtained, is soluble in concentrated sulfuric acid to a lue solution and yieldsa violet-blue Vat dyeing cotton fast blue tints. The final product has the following formula:

3. 10 parts of the brominating the anhydrideof perylene- 3.4.9.10-tetracarboxylic acid in ohlorosulfonic acid until 2 atoms of bromine are taken up and condensing the brominated aciduwith dyestufi, obtainable by ortho-phenylenedia-mine;-are heatedto the boilingpoint with parts-of phenol and 10 parts of anhydrous potassium. carbonate and boiling is continued for rl'Oho-urs while stirring. The melt can be worked up as described in Example 1. The dyestuflt' thus obtained is yery similar to that obtainable according to Example 2. The product has the following formula:

4. 5 parts of the: dyestuff obtainable by condensing d-chlorophenylenediamine-1.2

5. 10 parts of the dyestuficontaining chlorine, which is used in Example 2, are'heated to the boiling point with 100 parts of para toluidine and 10- parts of sodium carbonate and boiling is continued for 30 hours while stirring. After the melt has been cooled, it is diluted with alcohol, filtered and subsequently washed with alcohol and with water. The dried dyestufi" powder has a violetblack color, the hydrosulfite Vat is blue and dyes cotton Violet-blue'tints. The final product has the following formula:

In the present example the para-toluidine can also be replaced by other amines whereby valuable vat dyestufis are likewise obtained.

This application contains subject'matter in common with our application Ser. No.

681,273 filed on December'17,1923, which matured into Patent No. 4, 1929.

The following claims are not intended to compriseanything which has been claimed l1; our co-pending application Ser. No. 681,- 2 3. I p y We claim: 1. The process for producing vat dyestuffs consisting in condensing a compound of the following general formula:

wherein atleast one Y stands for chlorine, bromine or the nitro group and the remaining Ys for hydrogen, and one Z stands for chlorine and the other Zs for hydrogen with compounds of the general formula:

RX-I-I wherein X representsO, S or NH and R stands for an alkyl' or aryl group.

2. The process of producing Vat dyestuffs consisting in condensing a compound of the following general formula: V

j I Z Y i 1,715,430, dated June v .wherein at least one Y stands for chlorine, bromine or the nitro group and the remaining Yrs for hydrogen, and one Z stands for chlorine and the other Zs for hydrogen with a phenol.

3. The process of producing vat'dyestufis consisting in condensing a compound of the following formula:

with a phenol.

4. As new products the Vat dyestuffs of the following formula;

wherein at least one X stands for a substituent of the group consisting of NH NH-aryl, O-alkyl, O-aryl, S-alkyl and S-aryl and the other Xs for hydrogen, chlorine, bromine or a nitro group, and Z stands for hydrogen or chlorine, being bluish-black powders, soluble in concentrated sulfuric acid to green or blue solutions.

5. As new products the v t dyestuffs of the following formula:

wherein two Xs stand for O-aryl and the otherXsfor O-aryl or hydrogen, Z for chlorine or hydrogen, being bluish black powders, soluble in concentrated sulfuric acid to green or blue solutions.

6. As new products, the vat dyestuffs of the following formula:

bluish-black powders, soluble-in concentrated sulfuric acid to greenor blue solutions.

7. As new products, the vat dyestufis of the following formula:

36 wherein two Xs stand for O.C H and the other two Xs for 0.0 11 or hydrogen being bluish-black powders, soluble in concentrated sulfuric acid to green or blue solutions.

8. As a new product, the vat dyestufi' of the following formula:

being a bluish-black powder, soluble in con- 5 centrated sulfuric acid to a blue solution,

9. As a new product, the vat dyestufi' of the following formula:

N H. C7111 being a, Violet-black powder.

10. As a new product, the vat dyestuff of the following formula:

being a violet-black powder, soluble in contures.

MAXIMILIAN PAUL SCHMIDT. WILHELM NEUGEBAUER. 

